Polyoxometalate materials, metal-containing materials, and methods of use thereof

ABSTRACT

The invention relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H 5 PV 2 Mo 10 O 40 ; K 5 Si(H 2 O)Mn III W 11 O 39 ; K 4 Si(H 2 O)Mn IV W 11 O 39 ; or K 5 Co III W 12 O 40 . The invention further relates to a method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of the present invention with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. The invention further relates to a method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof. The invention further relates to a method for removing a contaminant from an environment, comprising contacting a modified material with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment, wherein the modified material comprises (1) a material and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The invention further relates to an article comprising the modified material of the present invention.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority upon U.S. provisional application Ser.No. 60/158,952, filed on Oct. 12, 1999, and the contents of which areherein incorporated by this reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to materials containing a polyoxometalateor a metal compound, wherein the metal compound is not apolyoxometalate. The invention further relates to methods for removing acontaminant from an environment by contacting the environment with apolyoxometalate material or a non-polyoxometalate material.

BACKGROUND OF THE INVENTION

Decreasing the potential danger of contaminants from the environment haslong been a significant issue. For example, the removal of offensiveodors originating from cigarette smoke, sweat, exhaust gases, and rottenfood in the work place, the home, and elsewhere would be quitebeneficial to the public-at-large. Additionally, materials that canremove highly toxic contaminants, such as chemical warfare agents(CWAs), from the environment can ultimately reduce a soldier's exposureto the agent. Examples of materials that would be useful include creams,powders, coatings, and fabrics.

Creams, also referred to as topical skin protectants (TSPs), have beendeveloped to protect soldiers from the threat of dermal exposure tochemical warfare agents. TSPs require an inert material which can beapplied on the skin in a thin layer to form an antipenetrant barrier toCWAs or other contact irritants that will not interfere excessively withnormal skin functions. A preferred TSP affords protection against CWAsand other toxic or irritating materials in all of the forms in whichthey might be encountered (e.g., liquid, aerosolized liquid and vapor).Perhaps the best-known vesicant CWA is 2,2′-dichlorodiethylsulfide (alsoknown as “HD” or “sulfur mustard”), which was first used during WorldWar I. Improved TSPs, however, are needed for protecting militarypersonnel and civilians from percutaneous exposure to CWAs andprotecting the skin from contact dermatitis arising from other sourcesas well.

U.S. Pat. No. 5,607,979 to McCreery discloses topical creams formed fromabout 35% to about 50% fine particulates of certainpoly(tetrafluoroethylene) (PTFE) resins dispersed in perfluorinatedpolyether oils having viscosities from about 20 cSt to about 350 cSt.The creams afford protection against chemical warfare agents such assulfur mustard (HD), lewisite (L), sulfur mustard/Lewisite mixtures(HL), pinacolyl methylphosphonofluoridate (soman or GD), thickened soman(TGD), and O-ethyl-S-2-diisopropylaminoethyl methylphosphonothiolate(VX). These creams, however, can only provide limited exposure to a CWAfor a short period of time. Furthermore, the creams cannot convert theCWA to an inactive form, which will reduce the overall toxicity of theCWA.

Thus, there is a need for a material, which is also referred to hereinas a support, that can remove a contaminant from the environment for anextended period of time. The incorporation of a polyoxometalate (hereinreferred to as “POM”) into a material such as a cream, coating, powder,or fabric, is one approach to removing a contaminant from an environmentGall et al. (Chem. Mat. 8, pp. 2523-2527, 1996) disclose theimmobilization of H₅PV₂Mo₁₀O₄₀ on carbon cloth in order to determine theability of H₅PV₂Mo₁₀O₄₀ to remove sulfur containing compounds fromtoluene. Johnson et al. (Proc. ERDEC Sci. Conf. Chem. Biol. Def. Res.,1998, pp. 393-399) disclose suspending H₅PV₂Mo₁₀O₄₀;K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; or K₅Co^(III)W₁₂O₄₀ ina perfluoropolyether barrier cream to determine the creams ability todetect the presence of mustard gas. Johnson et al., however, is notconcerned with the removal of the mustard gas from the gas phase.

The prior art also discloses the incorporation of polyoxometalates intopowders and coatings. For example, U.S. Pat. No. 5,356,469 to Curcio etal. disclose a metal pigment composition suitable for the formation of acoating composition. The coating composition is composed of a solvent, ametal pigment, at least one phosphosilicate pigment, and at least oneheteropoly anion. The metal pigment particles possess increasedstability against attack by water. Japanese patent application number4054127 to Terumo Corp. discloses the use of heteropoly acid salts asanti-tumor agents. The heteropoly acid salts can be administered in theform of a powder or suspended in solution. Although the prior artdiscloses a number of different applications of polyoxometalate powdersor coatings, the art does not disclose the use of a powder or coatingcontaining a polyoxometalate to remove a contaminant from theenvironment.

In light of the above, it would be very desirable to have an article anda method of using an article for the removal of toxic and/or malodorouscompounds without adding stoichiometric amounts of additives orcompounds to the article. The present invention solves such a need inthe art while providing surprising advantages. The present inventionherein incorporates a polyoxometalate (POM) into a material such as atopical carrier, powder, or coatings which greatly increases the abilityof the to remove a contaminant from the environment. The presentinvention also incorporates a metal compound, wherein the metal compoundis not a polyoxometalate, into a in order to remove a contaminant fromthe environment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the consumption of oxygen and formation of CEESO as afunction of time.

FIG. 2 shows CEESO formation as a function of time using 1Au/2Cu/3NO₃;2Cu/3NO₃; and 1Au/3NO₃.

SUMMARY OF THE INVENTION

In accordance with the purpose(s) of this invention, as embodied andbroadly described herein; this invention, in one aspect, relates to apolyoxometalate topical composition for removing a contaminant from anenvironment, comprising a topical carrier and at least onepolyoxometalate, with the proviso that the polyoxometalate is notH₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; orK₅Co^(III)W₁₂O₄₀.

The invention further relates to a method for removing a contaminantfrom an environment, comprising contacting the polyoxometalate topicalcomposition of the present invention with the environment containing thecontaminant for a sufficient time to remove the contaminant from theenvironment.

The invention further relates to a method for removing a contaminantfrom an environment, comprising contacting a polyoxometalate powder or apolyoxometalate coating with the environment containing the contaminantfor a sufficient time to remove the contaminant from the environment.

The invention further relates to a modified polyoxometalate, wherein themodified polyoxometalate comprises the admixture of (1) apolyoxometalate and (2) a cerium compound, a silver compound, a goldcompound, a platinum compound, or a combination thereof.

The invention further relates to a method for removing a contaminantfrom an environment, comprising contacting a modified material with theenvironment containing the contaminant for a sufficient time to removethe contaminant from the environment, wherein the modified materialcomprises (1) a material and (2) a metal compound comprising atransition metal compound, an actinide compound, a lanthanide compound,or a combination thereof, wherein the metal compound is not apolyoxometalate.

The invention further relates to a modified material for removing acontaminant from an environment, wherein the modified material comprises(1) a material comprising a topical carrier, a powder, a coating, or afabric, and (2) a metal compound comprising a transition metal compound,an actinide compound, a lanthanide compound; or a combination thereof,wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modified ofthe present invention.

Additional advantages of the invention will be set forth in part in thedescription which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations. It is to be understood that both theforegoing general description and the following detailed description areexemplary and explanatory only and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionand the Examples included therein.

Before the present methods and articles are disclosed and described, itis to be understood that this invention is not limited to specificsynthetic methods or to particular formulations, as such may, of course,vary. It is also to be understood that the terminology used herein isfor the purpose of describing particular embodiments only and is notintended to be limiting.

In this specification and in the claims which follow, reference will bemade to a number of terms which shall be defined to have the followingmeanings:

The singular forms “a,” “an” and “the” include plural referents unlessthe context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not.

In accordance with the purpose(s) of this invention, as embodied andbroadly described herein, this invention, in one aspect, relates to apolyoxometalate topical composition for removing a contaminant from anenvironment, comprising a topical carrier and at least onepolyoxometalate, with the proviso that the polyoxometalate is notH₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; orK₅Co^(III)W₁₂O₄₀.

The invention further relates to a modified polyoxometalate, wherein themodified polyoxometalate comprises the admixture of (1) apolyoxometalate and (2) a cerium compound, a silver compound, a goldcompound, a platinum compound, or a combination thereof.

The invention further relates to a modified material for removing acontaminant from an environment, wherein the modified material comprises(1) a material comprising a topical carrier, a powder, a coating, or afabric, and (2) a metal compound comprising a transition metal compound,an actinide compound, a lanthanide compound, or a combination thereof,wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modifiedmaterial of the present invention.

Many polyoxometalates known in the art can be used in the presentinvention to remove a contaminant from an environment. Polyoxometalatesare also referred to in the art as heteropoly compounds, heteropolyacids, isopoly compounds, and isopoly acids, which are subsets ofpolyoxometalates. Examples of polyoxometalates useful in the presentinvention are disclosed in Pope, M. T. in Heteropoly and IsopolyOxometalates, Springer Verlag, 1983, and Chemical Reviews, vol. 98, no.1, pp. 1-389, 1998, which are incorporated by this reference in theirentirety.

The selection of the polyoxometalate used in the present invention isdependent upon the contaminant or contaminants to be removed from theenvironment. In one embodiment, the polyoxometalate has the formula 1 of[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, m, and q is greater than zero, and A is one ormore different counterions. In one embodiment, s is from 19 to 460. Thecharge on the POM, y, is dictated by the values of k, m, n, o, p, q, rand s. The p-, d-, and f-block elements can exist in any oxidationstate.

Generally, M can be any d-block element having at least one d-electronor f-block element having at least one f-electron. Typically, Mcomprises titanium chromium, manganese, cobalt, iron, nickel, copper,rhodium silver, paladium, platinum, mercury, ruthenium cerium, oreuropium. In a preferred embodiment, M comprises manganese, cobalt, orruthenium. In another embodiment, X comprises phosphorus, silicon,aluminum boron, cobalt, zinc, or iron. When the polyoxometalate has theKeggin structure XM₁₂, then it is possible for X and at least one M tobe the same d- or f-block element. Not wishing to be bound by theory, itis believed that the metal ion M of the polyoxometalate of the presentinvention is responsible for removing the contaminant from the gasphase, while X, when present, provides structural integrity to thepolyoxometalate.

In one embodiment, the sum of k and q is greater than or equal to one,the sum of k, m, n, o, p, and q is 12, and s is 40. In yet anotherembodiment, k is not zero. In another embodiment, q is not zero.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(g+)V_(b) ^(j+)M_(c)^(h+)Z_(12-b-c) ^(i+)O_(x)]^(u−)[A], wherein X is at least one p-, d-,or f-block element; g is greater than or equal to 2; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; h is from 1 to 7; i is from 5 to 6; j is from4 to 5; x is 39 or 40; Z is tungsten, molybdenum, niobium, or acombination thereof; b is from 0 to 6; c is from 0 to 6; u is from 3 to9; and A is a counterion. The values of u, x, i, b, c, g, h, and j willvary depending upon the selection of X, M, and Z. The variables arerelated to one another and can be derived by the following formula:

u=2(x)−i(12-b-c)−g−c(h)−b(j)

The values of h, i, and j are average charges, and depend upon theselection and number of X, M, Z, and V present in the POM. For example,when Z is Nb⁺⁵ and Nb⁺⁶ (i.e., two Nb atoms present in the POM), thevalue of i+ is 5.5.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(g+)V_(b) ^(j+)Z_(12-b)^(i+)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon,aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and u is from3 to 9.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the structure [X^(g+)V_(b) ^(j+)Z_(12-c)^(i+)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon,aluminum, boron, zinc, cobalt, or iron; c is from 1 to 6, and u is from3 to 9.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)M_(v)^(t+)Z_(18-u-v) ^(y+)O_(z)]^(w−)[A], wherein X is at least one p-, d-,or f-block element; r is greater than or equal to 1; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; t is from 1 to 7; s is from 4 to 5; Z istungsten, molybdenum, niobium or a combination thereof; u is from 0 to9; v is from 0 to 9; y is from 5 to 6; z is 61 or 62; w is greater thanor equal to 4; and A is a counterion. Similar to the formula above, thevalues of r, s, t, u, v, w, y, and z, will vary depending upon theselection of X, M, and Z. The variables are related to one another andcan be derived by the following formula:

w=2(z)−y(18-u-v)−2r−v(t)−u(s)

The values of r, s, t, and y are also average charges, and depend uponthe selection and number of X, M, Z, and V atoms present in the POM.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)Z_(18-u)^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur,silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to 9; and wis greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X₂ ^(r+)M_(v) ^(t+)Z_(18-v)^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur,silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and wis greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [YV_(p)Z_(12-p)O₄₀][A], wherein Yis phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p isfrom 1 to 6, and A is a counterion. In one embodiment, Y is phosphorusand Z is molybdenum. In one embodiment, Y is phosphorus and Z istungsten. In one embodiment, Y is silicon and Z is molybdenum. In oneembodiment, Y is silicon and Z is tungsten. In one embodiment, Y isaluminum and Z is tungsten. In one embodiment, Y is aluminum and Z ismolybdenum.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(g+)V_(b) ^(h+)_(c)Z_(12-b-c)O₄₀]^(u−)[A], wherein X is at least one p-, d-, or f-blockelement; g+ is the charge of X; M is at least one f-block element ord-block element having at least one d-electron, wherein M is notvanadium; h+ is the charge of M; Z is tungsten, molybdenum, niobium, ora combination thereof; b is from 0 to 6; c is from 0 to 6, wherein thesum of b and c is greater than or equal to one; u is greater than 3; andA is a counterion.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(g+)V_(b)Z_(12-b)O₄₀]^(u−)[A],wherein X is at least one phosphorus, silicon, aluminum, boron, zinc,cobalt, or iron; Z comprises tungsten, molybdenum; niobium or acombination thereof; b is from 1 to 6; and u is greater than 3.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(g+)M^(h+)_(c)Z_(12-c)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon,aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenumniobium, or a combination thereof; M^(h+) is at least one f-blockelement or d-block element having at least one d-electron; c is from 1to 6; and u is greater than 3.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(i+) ₂V_(u)M^(j+)_(v)Z_(18-u-v)O₆₂]^(w−)[A], wherein X is at least one p-, d-, or f-blockelement; i+ is the charge of X; M is at least one d- or f-block element,wherein M is not vanadium; j+ is the charge of M; Z is tungsten,molybdenum, niobium, or a combination thereof; u is from 0 to 9; v isfrom 0 to 9, wherein the sum of u and v is greater than or equal to one;w is greater than or equal to 4; and A is a counterion.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(i+)V_(u)Z_(18-u)O₆₂]^(w−)[A],wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron,zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or acombination thereof; u is from 1 to 9; and w is greater than or equal to4.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [X^(i+) ₂M^(j+)_(v)Z_(18-v)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur,silicon, aluminum boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; M^(j+) is at least one d-or f-block element; v is from 1 to 9; and w is greater than or equal to4.

In a more specific embodiment, when the polyoxometalate has the formula1, the polyoxometalate has the formula [YV_(x)Z_(12-x)O₄₀][A], wherein Yis phosphorus, silicon, or aluminum, Z is tungsten or molybdenum; x isfrom 1 to 6, and A is a counterion. In one embodiment, Y is phosphorusand Z is molybdenum. In one embodiment, Y is phosphorus and Z istungsten. In one embodiment, Y is silicon and Z is molybdenum. In oneembodiment, Y is silicon and Z is tungsten. In one embodiment, Y isaluminum and Z is tungsten. In one embodiment, Y is aluminum and Z ismolybdenum.

Polyoxometalates having an organic group, such as an alkyl group or arylgroup, an organosilyl group, or other p- or d-block organometallicgroups bonded to the POM can also be used in the present invention. Theorganic group can be branched or straight chain alkyl, alkenyl, oralkynyl group or an aryl group of C₁ to C₃₀. The alkyl group can also bea polyether or polyol. Not wishing to be bound by theory, the organicgroup is bonded to the polyoxometalate as depicted in Scheme 1, where Ris the organic group and Met is generally vanadium, molybdenum,tungsten, niobium or tantalum:

The reaction between an alcohol and the polyoxometalate I results in theloss of water and the formation of the polyoxometalate II, wherein theorganic group is bonded to an oxygen atom of the polyoxometalate. Anyalcohol known in the art can be used in the present invention Examplesof alcohols that can be used include, but are not limited to, methanol,ethanol, or tris(hydroxymethyl)methane. The polyoxometalates havingorganic groups bonded to the POM that are disclosed in Gouzerh et al.,Chem. Rev., 98, pp. 77-111, 1998, which is incorporated by reference inits entirety, are useful in the present invention.

In another embodiment, the polyoxometalate I can be reacted with acompound having the generic formula YL_(o)R_(4-o), wherein Y is silicon,tin, or an other p- or d-block element; L is a leaving group; R is anorganic group, such as an alkyl, alkenyl, or alkynyl group or an arylgroup of C₁ to C₃₀; and o is from 1 to 4. Suitable leaving groups for Linclude, but are not limited to, halides and alkoxides. In Scheme I, theoxygen of polyoxometalate I displaces L from YLR₃ to form a new Y—O bond(compound III). Any silyl, tin, or organic derivative of a p- or d-blockelement known in the art can be used in the present invention, providedthat the compound has at least one leaving group.

The counterion A can be any counterion known in the art. Examples ofcounterions include, but are not limited to, quaternary ammonium cation,proton, alkali metal cation, alkaline earth metal cation, ammoniumcation, d-block cations, f-block cations, or a combination thereof. Inone embodiment, the polyoxometalate is an acid, wherein the counterion Ais hydrogen (H⁺). In one embodiment, the counterion is a d- or f-blockmetal complex. In one embodiment, the counterion istrimethyl-triazacyclononane manganese. In another embodiment, thecounterion A is hydrogen, lithium (Li⁺), sodium (Na⁺), potassium (K⁺),or a combination thereof. In another embodiment, A is not hydrogen orpotassium.

In another embodiment, the polyoxometalate comprises a modifiedpolyoxometalate, wherein the modified polyoxometalate comprises theadmixture of (1) a pre-modified polyoxometalate and (2) a ceriumcompound, a silver compound, a gold compound, a platinum compound, acopper compound, a cobalt compound, or a combination thereof. The term“admixture” can refer to the reaction product between thepolyoxometalate and the cerium compound, silver compound, gold compound,platinum compound, or a combination thereof. For example, the ceriumcompound, silver compound, gold compound, or platinum compound canundergo ion exchange with the counterion of the polyoxometalate. Thecerium compound, silver compound, gold compound, or platinum compoundcan also react with the polyoxometalate by a redox reaction. The term“admixture” can also refer to when the cerium compound, silver compound,gold compound, or platinum compound do not react at all with thepolyoxometalate. For example, the polyoxometalate may absorb the ceriumcompound, silver compound, gold compound, or platinum compound.

In one embodiment, when the POM is the sodium, lithium, or potassiumsalt or the acid form (A is H⁺), the POM can undergo ion exchange with acerium compound, a silver compound, a gold compound, a platinumcompound, or a combination thereof. For example, Ag₅PV₂Mo₁₀O₄₀ isproduced by the ion exchange of Na₅PV₂Mo₁₀O₄₀ with a stoichiometricamount AgNO₃. Any of the POMs described above can undergo ion exchangewith a cerium compound, a silver compound, a gold compound, a platinumcompound.

Depending upon the type and amounts of POM and cerium compound, silvercompound gold compound, or platinum compound used, the ion exchangereaction may or may not go to completion. When the ion exchange does notgo to completion, there may be small population of Na⁺, Li⁺, K⁺, or H⁺in the modified-polyoxometalate. For example, when H₅PV₂Mo₁₀O₄₀ isadmixed with AgNO₃, the resultant POM may be expressed by the formulaAg_(x)H_(5-x)PV₂Mo₁₀O₄₀, where x is from 1 to 5. Here, varying amountsof H⁺ may be present in the POM.

An example of a cerium compound useful in the present inventionincludes, but is not limited to, (NH₄)₂Ce(NO₃)₆. Examples of silvercompounds useful in the present invention include, but are not limitedto, AgNO₃ and AgClO₄. Examples of gold compounds useful in the presentinvention include, but are not limited to, HAuCl₄ and salts thereof. Anexample of a platinum compound useful in the present invention includes,but is not limited to, H₂PtCl₆.

In one embodiment, the counterion is cerium, silver, gold, platinum, ora combination thereof. In another embodiment, A is, independently,cerium, silver, gold, or platinum. In another embodiment, A is (1)cerium and silver; (2) cerium and platinum; (3) cerium and gold; or (4)silver and gold.

In another embodiment, A comprises (1) hydrogen, lithium, sodium,potassium, or a combination thereof, and (2) cerium, silver, gold,platinum, or a combination thereof.

In one embodiment, (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀;Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or a combination thereof,and (2) the cerium compound is (NH₄)₂Ce(NO₃)₆. In another embodiment,(1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀;Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the ceriumcompound is (NH₄)₂Ce(NO₃)₆; and (3) the gold compound is HAuCl₄. Inanother embodiment, (1) the pre-modified polyoxometalate isH₅PV₂Mo₁₀O₄₀; Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or acombination thereof; (2) the cerium compound is (NH₄)₂Ce(NO₃)₆; and (3)the platinum compound is H₂PtCl₆. In another embodiment, (1) thepre-modified polyoxometalate comprises Na₄PVMo₁₁O₄₀; Na₅PV₂Mo₁₀O₄₀;Na₆PV₃Mo₉₄O₄₀; Na₅H₂PV₄W₈O₄₀; Na₉PV₆Mo₆O₄₀; Na₅CuPW₁₁O₃₉; Na₅CuPW₁₁O₃₉;Na₅MnPW₁₁O₃₉; K₅CoPW₁₁O₃₉; (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂; or K₁₂Cu₃(W₉PO₃₄)₂,and (2) the gold compound is HAuCl₄. In another embodiment, (1) thepre-modified polyoxometalate is Na₅PV₂Mo₁₀O₄₀ and (2) the silvercompound is AgNO₃, AgClO₄, or a combination thereof.

In another embodiment, the polyoxometalate comprises K₈Co₂W₁₁O₃₉;K₈SiCoVW₁₀O₃₉; K₇SiCoVW₁₀O₃₉; Na₈Co₂W₁₁O₃₉; Ag₅PV₂Mo₁₀O₄₀; Ag₆PV₃Mo₉O₄₀;Ag₈CoVW₁₁O₄₀; Ag₁₂Ce(PW₁₁O₃₉)₂; Na₁₂Ce(PW₁₁O₃₉)₂; K₁₂Ce(PW₁₁O₃₉)₂;Na₅PCuW₁₁O₃₉; H₆PV₃Mo₉O₄₀; or K₅Cu^(II)PW₁₁O₃₉. In another embodiment,the polyoxometalate is not H₆PV₃Mo₉O₄₀.

Not wishing to be bound by theory, it is believed that some counterionsof the present invention can be reduced to the corresponding metal whenthe polyoxometalate contacts the contaminant. For example, when thecation is Ag⁺¹ or Au⁺³, these cations can be reduced to silver metal orAu⁺¹, respectively, depending upon the contaminant that is to beremoved. Thus, the counterion A can exist in multiple valence states.

The phrase “metal compound” refers to one or more transition metalcompounds, actinide compounds, lanthanide compounds, or a combinationthereof. When the metal compound is only one compound, then the materialis directly treated with the metal compound using techniques describedbelow. When the metal compound is composed of two or more compounds, thematerial can be sequentially treated with the compounds, oralternatively, the metal compounds can be admixed prior to treating thematerial with the metal compounds. Depending upon the metal compoundsthat are selected, the metal compounds may react with one another toform a new species, or they may not react at all with each other toproduce a composition or mixture. Materials that contain a metalcompound of the present invention are referred to herein as “non-POMmaterials.”

In one embodiment, the metal compound comprises a cerium compound, agold compound, a platinum compound, a silver compound, or a combinationthereof. Any of the cerium compounds, gold compounds, platinumcompounds, or silver compounds listed above can be used as the metalcompound. In another embodiment, the metal compound is a cerium compoundand a platinum compound, preferably (NH₄)₂Ce(NO₃)₆ and H₂PtCl₆,respectively. In another embodiment, the metal compound is a ceriumcompound and a gold compound, preferably (NH₄)₂Ce(NO₃)₆ and HAuCl₄,respectively. In another embodiment, the metal compound is a silvercompound and a gold compound, preferably AgNO₃ and/or AgClO₄ and HAuCl₄,respectively. In another embodiment, the metal compound is a ceriumcompounds, preferably (NH₄)₂Ce(NO₃)₆.

In another embodiment, the metal compound comprises (1) gold, copper,and nitrate; (2) gold, iron, and nitrate; (3) gold, manganese, andnitrate; (4) gold, titanium, and nitrate; (5) gold, cobalt, and nitrate;(6) gold and nitrate; (7) copper and nitrate; (8) iron and nitrate; (9)gold, vanadium, and nitrate; (10) gold, nickel, and nitrate; (11) gold,silver, and nitrate; or (12) gold, chloride, and nitrate. In a preferredembodiment, the metal compound comprises gold, chloride, and nitrate. Inanother embodiment, the metal compound comprises mixing (NEt₄)AuCl₂ withvarying amounts of CuSO₄, MnSO₄, VOSO₄; Ti(SO₄)₂, Fe(SO₄)₃, NiSO₄,ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃, and/or NBu₄NO₃. Inanother embodiment, the metal compound is produced by mixing (NEt₄)AuBr₂and NBu₄NO₂.

When the metal compound comprises two or more compounds, the compoundscan be admixed using techniques known in the art. In one embodiment, themetal compound can be produced by admixing two or more metal salts. Theanion of the salt can be any anion known in the art. Examples of anionsinclude, but are not limited to, sulfate, carbonate, acetate, nitrate,chloride, and stearate. In one embodiment, when two or more compoundsare used to produce the metal compound, the compounds are mixed in thepresence of a solvent, preferably an organic solvent. In one embodiment,After the compounds have been sufficiently admixed, the solvent isremoved, and the metal compound is optionally dried. In one embodiment,the drying step is by vacuum.

Any POM or metal compound of the present invention can be incorporatedinto a material in order to remove a contaminant from the environment.Examples of materials include, but are not limited to, a topicalcarrier, a coating, a powder, or a fabric. As described above, amaterial as used herein refers to a support that holds the POM or metalcompound.

In one embodiment, the polyoxometalate and the metal compound can beincorporated sequentially into the material. In one embodiment, thepolyoxometalate is incorporated into the material-followed by theincorporation of the metal compound into the material. In anotherembodiment, the metal compound is incorporated into the materialfollowed by the incorporation of the polyoxometalate into the material.

A wide variety of topical carriers can be used in the present invention.Suitable topically acceptable pharmaceutical carriers are those whichtypically are used in the topical application of pharmaceuticals andcosmetics. Examples of such carriers include, but are not limited to,lotions, creams, ointments, and gels. Topical carriers are also referredto in the art as barrier creams and topical skin protectants. Any of thetopical carriers disclosed in U.S. Pat. No. 5,607,979 to McCreery can beused in the present invention, which is incorporated by reference in itsentirety. In one embodiment, the topical carrier comprises aperfluorinated polymer. In another embodiment, the topical carriercomprises a perfluoropolyether. An example of a perfluoropolyether(PFPE) useful in the present invention has the general formulaCF₃O[—CF(CF₃)CF₂O—]_(x)(—CF₂O—)_(y)CF₃). In one embodiment, the topicalcarrier comprises a perflourinated polymer and one or more unfluorinatedpolymers. In another embodiment, the topical carrier comprises aperfluoropolyether and one or more unfluorinated polyethers.

In one embodiment, the topical carrier may further contain saturated orunsaturated fatty acids such as stearic acid, palmitic acid, oleic acid,palmito-oleic acid, cetyl or oleyl alcohols, stearic acid, fluorinatedacids, fluorinated alcohols (e.g., tetrafluoroethanol), or combinationsthereof. The cream may also optionally contain one or more surfactants,such as a non-ionic surfactant.

In one embodiment, the polyoxometalate topical composition is composedof a perfluoropolyether and the counterion A of the POM is silver. Inanother embodiment, the polyoxometalate topical composition is composedof a perfluoropolyether and the metal compound is a silver compound agold compound, or a combination thereof. In another embodiment, thenon-POM material comprises a topical carrier composed of aperfluoropolyether and the metal compound comprises a silver compound,preferably AgNO₃ or AgClO₄.

In another embodiment, the non-POM topical composition is composed aperfluoropolyether and the metal compound comprises a cerium compound, asilver compound, a palladium compound, a platinum compound, or a silvercompound.

A wide variety of powders and coatings known in the art can be used asthe material of the present invention. Intone embodiment, the powdercomprises activated carbon.

Any fabric known in the art can be used to produce a polyoxometalatefabric or non-POM fabric of the present invention. In one embodiment,fabrics used to prepare garments, draperies, carpets, and upholstery canbe used and articles made from them are a part of this invention. Inanother embodiment, the fabric can be a knit or non-woven fabric. Usefulfibers include, but are not limited to, polyamide, cotton, polyacrylic,polyacrylonitrile, polyester, polyvinylidine, polyolefin, polyurethane,polytetrafluoroethylene, or carbon cloth, or a combination thereof. Inone embodiment, the fabric is prepared from cotton, polyacrylic, orpolyacrylonitrile. In one embodiment, the fabric is prepared from acationic fiber. In another embodiment, the fabric comprises (1) a 50/50blend of nylon-6,6 and cotton or (2) stretchable carbon blended withpolyurethane.

Any cellulosic fiber can be incorporated by a POM or metal compound toproduce the polyoxometalate fibers or non-POM fibers of the presentinvention. Examples of useful cellulosic fibers include, but are notlimited to, wood or paper. In a preferred embodiment, a polyoxometalateor the metal compound of the present invention can be incorporated inpaper in order to remove a contaminant from the gas or liquid phase. Inone embodiment, the paper is wallpaper.

The amount of polyoxometalate or metal compound incorporated into thematerial varies depending upon the contaminant to be removed and thematerial that is selected. There is no restriction on the amount of POMor metal compound that can be incorporated into the material. In oneembodiment, the amount of polyoxometalate or metal compound incorporatedin the material is from 0.1 to 95% by weight of the polyoxometalatematerial or non-POM material. In one embodiment, the lower limit ofpolyoxometalate or metal compound by weight is 0.1, 0.5, 1.0, 2.0, 5.0,10, 15, 20, 25, 30, 35, 40, 45, or 50%, and the upper limit is 30, 40,50, 60, 70, 80, 90, or 95%. In one embodiment, when the material is atopical carrier, the polyoxometalate or metal compound is from 5 to 30%by weight of topical composition.

The present invention is capable of removing a single contaminant ormultiple contaminants from an environment. The term “environment” asused herein refers to any media that contains at least one contaminant.In one embodiment, the environment comprises a liquid phase. In anotherembodiment, the environment comprises a gas phase.

The term “remove” refers to, but is not limited to, the degradation ofthe contaminant, the conversion of the contaminant into another compoundthat is either less toxic or nontoxic and/or malodorous, or theadsorption of the contaminant by the polyoxometalate or the metalcompound. The POM and metal compound can degrade the contaminant by anumber of different mechanisms. For example, the POM can aerobicallyoxidize the contaminant acetaldehyde (CH₃CHO). Not wishing to be boundby theory, it is believed that the aerobic oxidation of CH₃CHO proceedsby a radical chain mechanism (i.e., the initiation of the radical chainby CH₃CHO+POM_(ox)->CH₃CO.+HPOM_(red)).

Contaminants that can be removed by using the present invention include,but are not limited to, an aldehyde, an aliphatic nitrogen compound, asulfur compound, an aliphatic oxygenated compound, a halogenatedcompound, an organophosphate compound, a phosphonothioate compound, aphosphorothioate compound, an arsenic compound, a chloroethyl-aninecompound, a phosgene compound, a cyanic compound, or a combinationthereof. In one embodiment, the contaminant is acetaldehyde, methylmercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide,diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine,styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valericacid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide, carbonmonoxide, or a combination thereof. In another embodiment, thepolyoxometalate materials and non-polyoxometalate materials can removemicrobial life from the gas or liquid phase. Examples of microbial lifeinclude, but are not limited to, bacteria, protozoa, and viruses.

In another embodiment, the contaminant is a chemical warfare agent(CWA). The chemical warfare agents disclosed in Marrs, Timothy C.;Maynard, Robert. L; Sidell, Frederick R.; Chemical Warfare AgentsToxicology and Treatment; John Wiley & Sons: Chichester, England, 1996;Compton, James A. F. Military Chemical and Biological Agents Chemicaland Toxicological Properties; The Telford Press: Caldwell, N.J., 1988;Somani, Satu M. Chemical Warfare Agents; Academic Press: San Diego.1992, which are herein incorporated by reference in their entirety, canbe removed by the polyoxometalate materials of the present invention.

The present invention can remove a contaminant from the environment inthe gas phase under mild conditions. In one embodiment, the contaminantcan be removed from −50° C. to 250° C. at a pressure of from 0.1 ppb to30 atm, preferably from 25° C. 20 to 105° C. at 1 atm. In anotherembodiment, the lower temperature limit is −50, −40, −30, −20, −10, 0,10, 20, 50, 75, 100, or 150° C., and the upper temperature limit is 50,75, 100, 125, 150, 175, 200, 225, or 250° C. In a preferred embodiment,the present invention can remove a contaminant from the environment atroom temperature (approximately 25° C.) and at 1 atm. In anotherembodiment, the present invention can remove a contaminant from the gasphase that has a partial pressure of from 0.1 ppb to 2 atm, 10 ppb to 2atm 100 ppb to 2 atm, 200 ppb to 2 at, and 0.5 ppm to 2 atm. Similarly,the present invention can remove a contaminant under mild conditionswhen the environment is a liquid phase. In one embodiment, thecontaminant can be removed from a liquid media at from 0° C. to 200° C.The temperature depends upon the liquid media that is being contactedand the contaminant to be removed.

The POMs and metal compounds are typically used in the presence of anoxidizer to remove a contaminant from the environment. In oneembodiment, the POMs and/or metal compounds are used in the presence ofair, which oxidizes the POM and/or metal compound. In anotherembodiment, additional oxidizers can be used in combination with air tooxidize the POM and/or metal compound. Examples of oxidizers include,but are not limited to, peroxides and peracids. In a preferredembodiment, air is used as the oxidizer.

The environment containing the contaminant can be contacted by thepolyoxometalate materials or non-POM materials using a variety oftechniques. For example, when the contaminant is in the liquid phase,the polyoxometalate material or non-POM material can be dipped orsubmersed into the liquid phase. Alternatively, the liquid phase can befiltered or passed through the polyoxometalate material or non-POMmaterial. When the contaminant is in the gas phase, the polyoxometalatematerial or non-POM material is typically placed in an open or closedenvironment that contains the contaminant(s).

The polyoxometalate materials or non-POM materials of the presentinvention have a number of advantages over the prior art materials thatdo not use a polyoxometalate to remove a contaminant from theenvironment. One advantage is that the present invention can remove acontaminant from the environment starting within milliseconds of contactand can remove the contaminant for extended periods of time, rangingfrom several days to indefinitely. The POMs and metal compounds used inthe present invention are capable of being regenerated to an active formthat permits the removal of the contaminant. Another advantage is thatsome POMs and metal compounds can render the material more waterresistant and increase the surface area of the material. Finally, whenthe material is a fabric or cellulosic fiber, the POM and metal compoundcan enhance the dyeability, light fastness, color fastness, and weavingproperties of the fabric or cellulosic fiber.

The polyoxometalate and metal compound can be, incorporated into thematerial using techniques known in the art. In one embodiment, when thematerial is a topical carrier, powder, or coating, the polyoxometalateor metal compound is directly added to and admixed with the material. Inanother embodiment, the material (topical carrier, powder, coating, orfabric) is contacted with a mixture comprising the polyoxometalate ormetal compound and a solvent. The polyoxometalate or metal compound canbe soluble, partially soluble, or insoluble in the solvent, dependingupon the polyoxometalate or metal compound and solvent selected. In oneembodiment, the solvent is water. In another embodiment, the solvent canbe an organic solvent. Examples of organic solvents useful in thepresent invention include, but are not limited to, acetonitrile,acetone, toluene, carbon dioxide, xylenes, 1-methyl-2-pyrrolidinone,dimethyl sulfoxide, or an alcohol, such as methanol, ethanol,1-propanol, or 2-propanol.

In one embodiment, when the material is a fabric or cellulosic fiber,the polyoxometalate or metal compound mixture is from 0.1 to 20% byweight polyoxometalate or metal compound and from 80 to 99.9% by weightwater, preferably from 0.3 to 15% by weight polyoxometalate or metalcompound and 85 to 99.7% water. Generally, the fabric or cellulosicfiber is dipped or immersed into the mixture containing the POM or metalcompound for several hours to days at a temperature of from 0° C. to100° C., preferably for 2 hours to 2 days at from 25° C. to 80° C. Inanother embodiment, the POM or metal compound can be admixed with aresin or adhesive, and the resultant adhesive is applied to the surfaceof or admixed with the fabric or cellulosic fiber.

Typically, once the material has been contacted with the POM or metalcompound mixture, the polyoxometalate material or non-POM material isdried in order to remove residual solvent. In one embodiment, thepolyoxometalate materials or non-POM material is heated from 0° C. to220° C. at or below atmospheric pressure, preferably from 25° C. to 100°C. In another embodiment, the polyoxometalate material or non-POMmaterial is dried in vacuo (i.e., less than or equal to 10 torr).

In another embodiment, when the material is a fabric or cellulosicfiber, the POM or metal compound can be incorporated into the fabric orcellulosic fiber by depositing the POM or metal compound on the surfaceof an existing fabric or cellulosic fiber, covalently bonding the POM ormetal compound to the fibers of the fabric or cellulosic fiber,impregnating or intimately mixing the POM or metal compound with thefabric or cellulosic fiber, electrostatically bonding the POM or metalcompound to the fabric or cellulosic fiber, or datively bonding the POMor metal compound to the fabric or cellulosic fiber via the coordinationof a d- or f-block metal ion on the surface of the POM or metal compoundwith a functional group on the fabric. In the case of electrostaticallybonding the POM to the fabric or cellulosic fiber, the positivelycharged functional groups on the fabric or cellulosic fiber and thenegatively charged POM can form an electrostatic bond. In oneembodiment, when the counterion of the polyoxometalate is a proton orthe metal compound is an acid, the fabric or cellulosic fiber can beprotonated by the polyoxometalate or metal compound to produce apositively charged fiber, which then electrostatically bonds to thepolyoxometalate or metal compound anion. In one embodiment, a cationicpolymer can be used as a binding agent to incorporate an anionicpolyoxometalate or metal compound into an anionic fiber.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompositions, materials, and methods claimed herein are made andevaluated, and are intended to be purely exemplary of the invention andare not intended to limit the scope of what the inventors regard astheir invention. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperature, etc.) but some errors anddeviations should be accounted for. Unless indicated otherwise, partsare parts by weight, target odorants/toxics are expressed in parts permillion, temperature is in ° C. or is at ambient temperature andpressure is at or near atmospheric.

The term “consumption” or “consumed” refers to the removal or adsorptionof a contaminant or contaminants from the environment or the conversionof the contaminant or contaminants to another compound that is nontoxicand/or non-malodorous.

General Considerations

Materials. PFPE #1511 is composed of 35-50% polytetrafluoroethylenethickening agent dispersed in a perfluoropolyether oil with water as aco-surfactant. PFPE #1511 was provided by Dr. E. H. Braue of the UnitedStates Army Medical Research Institute for Chemical Defense.

All reagents used in the examples were obtained from Aldrich ChemicalCompany, Milwaukee, Wis., and were used without further purification.The following reagents were used in the examples (the purity of thereagent is in parenthesis): CEES (98%), HPLC grade acetonitrile,tetrafluorethylene (99.5%), 1,3-dichlorobenzene (98%), dimethylsulfoxide (DMSO) (99.8%), AgNO₃ (99+%), HAuCl₄ (99+%), CuCl₂ (99+%),FeCl₃ (98%), AgClO₄ (99.9%), (NEt₄)AuCl₂, CuSO₄ (99.99%), MnSO₄ (98%),VOSO₄ (99.99%), Ti(SO₄)₂ (99%), Fe₂(SO₄)₃ (97%), NiSO₄ (99%), ZnSO₄(99%), Cr₂(SO₄)₃ (99.999%), MgSO₄ (99%), CoSO₄ (99.998% Y, Pd(NO₃)₄(98%), Na₂SO₃ (99%), and NBu₄NO₃ (97%). NBu₄NO₂ (98%) was purchased fromFluka.

Synthesis of Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀

Na₅PV₂Mo₁₀O₄₀ was prepared by the literature procedure outlined inPetterson, L.; Andersson, I.; Selling, A.; Grate, J. H. Inorg. Chem.1994, 33, 982. Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀ was prepared using the followingprocedure. Ground H₅PV₂Mo₁₀O₄₀ (30.9 g, 1.78×10⁻² mol) was dissolved in200 mL of distilled water. The orange solution was filtered three timesto remove any undissolved POM. Ground AgNO₃ (15.2 g, 8.94×10⁻² mol) wasadded with vigorous stirring. The mixture was stirred overnight at roomtemperature. The product precipitated as a dark red-orange powder andwas removed by suction filtration over a medium fritted glass funnel.The product was dried in vacuo overnight. The IR spectrum of theresultant powder confirmed the formation of Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀.

Synthesis of Additional Polyoxometalates

The following POMs listed in Table 8 were prepared by literatureprocedures (the entry number in Table 8 and the bibliographicalinformation are in parenthesis):

-   Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₃₉; K₅MnPW₁₁O₃₉; and K₅CoPW₁₁O₃₉: (Entries    2-4 and, 6, respectively; Maksimov, G. M.; Kustova, G. N.;    Matveev, K. I.; Lazarenko, T. P Koord. Khim. 1989, 15(6), 788-96).-   Na₅PV₂Mo₁₀O₄₀ and H₅PV₂Mo₁₀O₄₀: (Entries 7 and 20, respectively;    O'Donnell, Stephen E.; Pope, Michael T. J. Chem. Soc., Dalton Trans.    1976, 21, 2290-7).-   Na₄PVMo₁₁O₄₀: (Entry 11; So, Hyunsoo; Pope, Michael T. Inorg. Chem.    1972, 11(6), 1441-3).-   Na₆PV₃Mo₉O₄, and H₆PV₃Mo₉O₄₀ (Entries 8 and 21, respectively; Pope,    Michael T.; O'Donnell, Stephen E.; Prados, Ronald A. J. Chem. Soc.,    Chem. Commun. 1975, 1, 22-3).-   Na₅H₂PV₄Mo₈O₄₀ and H₇PV₄Mo₈O₄₀: (Entries 9 and 22, respectively;    Yurchenko, E. N. J. Mol. Struct. 198.0, 60, 325-31).-   Na₅FeSiW₁₁O₃₉ and K₆FeSiW₁₁O₃₉: (Entries 12 and 36, respectively;    Peacock, R. D.; Weakley, T. J. R. J. Chem. Soc. A 1971, 12,    1937-400).-   Na₅SiVW₁₁O₄₀: (Entry 13; Tourne, Claude; Tourne, Gilbert. Bull. Soc.    Chim. Fr. 1969, 4, 1124-36).-   K₈Co(II)P₂W₁₇O₆₁: (Entry 15; Marcu, Gheorghe; Patrut, Adrian; Botar,    Alexandru. Rev. Chim. (Bucharest) 1989, 40(11), 870-5).-   K₁₂Pd₃(PW₉O₃₄)₂: (Entry 16; Kuznetsova, N. I.; Kuznetsova, L. I.;    Detusheva, L. G.; Likholobov, V. A.; Fedotov, M. A.; Koscheev, S.    V.; Burgina, E. B. Stud. Surf. Sci. Catal. 1997, 110 (3rd World    Congress on Oxidation Catalysis, 1997), 1203-1211).-   K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Hamlaoui, Mohamed Larbi; Vlassenko,    Konstantin; Messadi, Djelloul. C. R. l'Academie Sci., Ser. II    Univers 1990, 311(7), 795-8).-   Na₄PVMo₁₁O₄₀ and Na₃PMo₁₂O₄₀: (Entries 18 and 19, respectively; So,    Hyunsoo; Pope, Michael-T. Inorg. Chem. 1972, 11(6), 1441-3).-   Na₁₆P₄W₃₀Cu₄O₁₁₂: (Entry 24; Huang, Ru-Dan; Bei; Bao-Li; Wang,    En-Bo; Li, Bai-Tao; Zhang, Su-Xia. Gaodeng Xuexiao Huace Xuebao    1998, 19(11), 1721-1723).-   K₁₀Ce(PW₁₁O₃₉)₂: (Entry 26; Peacock, R. D.; Weakley, T. J. R. J.    Chem. Soc. A 1971, 12, 1937-40).-   K₇CuSiW₁₁O₃₉ and Na₇CuSiW₁₁O₃₉: (Entries 27 and 30, respectively;    Teze, Andre; Souchay, Pierre. C. R. Acad. Sci, Ser. C 1973, 276(19),    1525-8).-   Na₅NiPW₁₁O₃₉: (Entry 31; Maksimov, G. M.; Kustova, G. N.;    Matveev, K. I.; Lazarenko, T. P. Koord Khim. 1989, 15(6), 788-96).-   Na₃AsW₁₂O₄₀: (Entry 35; Tsyganok, L. P.; Statsenko, V. P.;    Vil'dt, A. L. Zh. Neorg. Khim. 1974, 19(11), 3071-7).-   K₈NiP₂W₁₇O₆₁: (Entry 37; Hamlaoui, Mohamed Larbi; Vlassenko,    Konstantin; Messadi, Djelloul C. R. l'Academie Sci., Ser. II Univers    1990, 311(7), 795-8).-   (Me₄N)₁₀(Co₃SiW₉O₄H₆): (Entry 38; Nomiya, Kenji; Miwa, Makoto.    Polyhedron 1985, 4(8), 1407-12).-   Na₃V₁₀O₂₈: (Entry 40; Preuss, F.; Rosenhahn, L. J. Inorg. Nucl.    Chem. 1972, 34(5), 1691-703).-   K₈P₂W₁₇(NbO₂)O₆₁: (Entry 42; Gong, Jian; Li, Guoping; Wang, Fuquan;    Qu, Lunyu. Wuji Huaxue Xuebao 1995, 11(3), 232-7).-   (NH₄)₆P₂FeW₁₇O₆₁: (Entry 43; Peacock, R. D.; Weakley, T. J. R. J.    Chem. Soc. A 1971, Issue 12, 1937-40).-   K₇Mn(II)P₂W₁₇O₆₁: (Entry 44; Marcu, Gheorghe; Patrut, Adrian; Botar,    Alexandru. (1). Rev. Chim. (Bucharest) 1989, 40(11), 870-5).-   (NH₄)₆P₂W₁₈O₆₂: (Entry so; Varga, Gideon M., Jr.; Papaconstantinou,    Elias; Pope, Michael T. Inorg. Chem. 1970, 9(3), 662-7).-   Na₉PV₆Mo₆O₄₀: (Entry 1; Ret'yakov, V. P.; Volkova, L. K.;    Zimtseva, G. P.; Rudakov, E. S. Kinet. Katal. 1993, 34(1), 183).-   K₁₂Cu₃(W₉PO₃₄)₂: (Entry 10; Weakley, Timothy J. R.; Finke,    Richard G. Inorg. Chem. 1990, 29(6), 1235-41).-   K(NH₄)₆RuBW₁₁O₃₉: (Entry 34; Liu, Huizhang; Sun, Werliang; Yue, Bin;    Li, Mingxing; Chen, Zhijiang; Jin, Songlin; Xie, Gaoyang; Shao,    Qianfen; Wu, Tailiu; Chen, Shiming; Yan, Xiaoming. Wuji Huaxue    Xuebao 1997, 13(3), 251-257).-   K₁₀Ni₄P₂W₁₇O₆₁: (Entry 14; Yon, David K.; Miller, Warren K; Novet,    Thomas; Domaille, Peter J.; Evitt, Eric; Johnson, David. C.; Finke,    Richard G. J. Am. Chem. Soc. 1991, 113(19), 7209-21).-   K₁₀Co₄P₂W₁₈O₆₈: (Entry 39; Evans, Howard T.; Tourne, Claude M.;    Tourne, Gilbert F.; Weakley, Timothy J. R. J. Chem. Soc., Dalton    Trans. 1986, 12, 2699-705).-   K10Mn4(PW₉O₃₄)₂: (Entry 41; Gomez-Garcia, C. J.; Coronado, B.;    Gomez-Romero, P.; Casan-Pastor, N. Inorg. Chem. 1993, 32(15),    3378-81).-   K₁₂Cu₄P₂W₁₈O₆₈: (Entry 45; Weakley, Timothy J. R.; Finke, Richard G.    Inorg. Chem. 1990, 29(6), 1235-41).-   K₁₂P₂W₁₈Ni₃O₆₈: (Entry 47; Gomez-Garcia, Carlos J.; Coronado,    Eugenio; Ouahab, Lahcene. Angew. Chem. 1992, 104(5), 660-2).-   Na₆P₄W₃₀Mn(II)₄O₁₁₂ (Entry 49; Gomez-Garcia, C. J.;    Borras-Almenar, J. J.; Coronado, E.; Ouahab, L. Inorg. Chem. 1994,    33(18), 4016-22).-   K₈Co₂W₁₁O₃₉: (Entry 29; Walmsley, F. J. Chem. Ed. 1992, 69(11),    936-38).-   (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆: (Entry 51; Minami, N.; Hiraoka, M.; Izumi,    K.; Uchida, Y. Japanese Patent JP 08113731 A2 1996, Chem. Abstr.    1996, 125, 117542).-   Na₃H₃PMo₉O₃₄: (Entry 48; Inouye, Y.; Tokutake, Y.; Kunihara, J.;    Yosbida, T.; Yamase, Y.; Nakata, A.; Nakamura, S. Chem. Pharm. Bull.    1992, 40, 805-807).-   K₈CoVW₁₁O₄₀: (Entry 28; Bas-Serra, J.; Todorut, et al. Synth. React.    Inorg. Met.-Org. Chem. 1995, 25(6), 869-82).-   H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂]: (Entry 25; Shigeta, S.; Mod,    S.; Watanbe, J.; Baba, M.; Khenkin, A. M.; Hill, C. L.;    Schinazi, R. F. Antiviral Chem. Chemother. 1996, 346-352).-   K₆SiTiW₁₀O₄₀: (Entry 33; Blasecki, J. W. Top. Mol. Org. Eng. 1994,    10, 373-385).-   K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Marcu, Gheorghe; Patrut, Adrian; Botar,    Alexandru. Rev. Chim. (Bucharest) 1989, 40(11), 870-5).-   (n-Dec₄)₆HMnNb₃P₂W₁₀O₆₂: (Entry 5; Gong, J., Chen, et al.    Polyhedron, 1996, 15, 2273-7).    The following POMs were prepared by the following experimental    procedures.

K₅Si(NbO₂)W₁₀O₄₀ (Entry 46): 0.1.0 g of K₇HNb₆O₁₆ was dissolved in 75-mLof deionized H₂O. To this solution, 2-mL of 30% H₂O₂ was added. A fewdrops of 3M HCl were added to bring the pH to approximately 6.K₈SiW₁₁O₃₉ (15.8 g) was added, which resulted in gas evolution. To theswirling mixture, 25-mL of H₂O followed by 12-mL of 3M HCl were added.The color of the solution was yellow and the pH was approximately 1. Themixture was stirred for an additional 30 minutes, then 14 g of solid KClwas added, which resulted in the formation of a pale yellow solid. Thesolid was collected by filtration and dried resulting in 4.7 g ofK₅Si(NbO₂)W₁₁O₄₀.

Na₆SiVNbW₁₁O₃₉ (Entry 32): 6.64 g of K₇Hb₆O₁₉ was dissolved in 800-mL ofH₂O. To this solution, 80-mL of 30% H₂O₂ solution was added and the pHwas adjusted to 6.0 with KOH. Solid K₉SiVW₁₀O₃₉ was added slowly toproduce a final pH of 8.5. To this mixture, 40-mL of 3M HCl was addeddropwise. The addition was stopped occasionally to agitate the solid.The solution was then stirred for 15 minutes. Additional 3M HCl (40-mL)was added to give a pH of 1.5. The solution was stirred for 1 hour, and160 g of solid KCl was added. The orange precipitate was filtered offand dried, yielding 40.85 g of K₆SiVNbW₁₁O₃₉. K₆SiVNbW₁₁O₃₉ and waterwere passed through an Amberlite IR-120 ion exchange column which wascharged with 1 M NaCl. The volatiles were removed from the collectedsolution by vacuum to produce Na₆SiVNbW₁₁O₃₉ as a yellow, crystallinesolid. The Amberlite is a product of Rohm and Haas and was purchasedfrom Aldrich.

Instrumentation. Gas chromatography analysis was conducted using aHewlett-Packard Series 5890 Gas Chromatograph equipped with a flameionization detector and fitted with a non-polar 5% PHME siloxane, 30meter column. Alternatively, the gas chromatograph was equipped with anFID detector and a 5% phenyl methyl silicone capillary column Massabundance determinations were performed using a HP 5890 GC with a 5%phenyl methyl silicone capillary column and a 5971A Mass SelectiveDetector. Gas chromatography/mass spectroscopy was performed using aHewlett-Packard Series II 5890 Gas Chromatograph equipped with a 5971Amass selective detector and fitted with a non-polar 5% PHME siloxane, 25meter column. For both GC and GC-MS, nitrogen was used as the carriergas. In Examples 5 and 6, all reactions were monitored using aHewlett-Packard 6890 gas chromatograph with flame ionization detectorand HP-5 (5% phenylmethylsilicone capillary column. UV-visible spectrawere run on a HP 8452A Diode Array Spectrophotometer. The percentages ofO₂ of the reaction atmosphere were varied using a Series 810 Mass Trakflowmeter with dried argon as the other gas.

Example 1 Oxidation of CEES to CEESO by a POM/TSP Mixture Under AmbientConditions after 40 Days

PFPE #1511 (0.525 g) was combined with Ag_(x)Na_(5-x)PV₂Mo₁₀O₄₀ (0.066g, 3.81×10⁻⁵ mol) to give a 11% weight/weight POM/cream mixture. ThePOM/cream mixture was placed in a 18 mL glass vial fitted with apoly(tetrafluoroethylene) (PTFE) stopper. A sufficient amount of2-chloroethyl ethyl sulfide (CEES) was added to the mixture tocompletely submerge the POM/cream mixture. After 40 days, 10 μL of theCEES solution surrounding the POM/cream mixture was removed and dilutedinto 100 μL of 2,2,2-trifluoroethanol (TFE). GC-MS of this solutionshowed the presence of 2-chloroethyl ethyl sulfoxide (CEESO).

Example 2 Oxidation of CEES to CEESO by POM/TSP Mixtures Under AmbientConditions

The CEES composition used in all trials was composed of 9.0 mL of CEEScombined with 100 μL of 1,3-dichlorobenzene, where the1,3-dichlorobenzene was added as an internal reference. Each POM/PFPE#1511 cream mixture (approximately 0.3 g) was smeared at the bottom ofan 18 mL glass vial and fitted with a PTFE cap. The CEES composition(1.0 mL) was then added and each vial was left undisturbed for severaldays under ambient conditions, with periodic GC analysis of theCEES/reference solution to check for CEESO formation. For GC analysis,10 μL of the CEES/reference solution surrounding the POM/cream mixturewas diluted in 100 μL of TFE and analyzed. The results are shown inTable 1.

TABLE 1 Weight Turnovers after Entry Catalyst Percent^(a) 9 Days^(b) 1cream only N/A 0 2 AgNO₃ 20.3% 0 3 H₅PV₂Mo₁₀O₄₀ 5.8% 0 4 H₅PV₂Mo₁₀O₄₀20.8% 0 5 Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀ 5.6% 0 6 Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀20.6% 0 7 HAuCl₄ 7.1% 0 8 HAuCl₄, AgNO_(3,) 7.6% 5 AgClO₄ ^(c)^(a)Weight Percent = (mass of POM (g))/(mass of cream (g) + mass of POM(g)) × 100 ^(b)Turnovers = (mol of CEESO/mol of catalyst) × 100 ^(c)Thismixture was composed of 1 equiv. of HAuCl₄, 1.25 equiv. of AgClO₄, and0.75 equiv. of AgNO₃. The weight percent is reported as the (weight ofall components, g)/(weight of cream, g + weight of components, g) × 100

Example 3 Catalytic Oxidation of CEES by POMs in 2,2,2-Trifluoroethanolafter 14 Days Under Ambient Conditions

A CEES solution was prepared by mixing 85.8 mM of CEES; 1.51×10⁻⁵ to1.82×10⁻⁵ mmol of catalyst; 100 μL 1,3-dichlorobenzene (internalstandard); and 85 mL of 2,2,2-trifluoroethanol, at 25° C. under ambientair. In a typical run, 5.0 mL of the CEES solution was combined withenough catalyst to yield a CEES:POM ratio of 20:1, and the mixture wasstirred for 14 days. The results are shown in Table 2.

TABLE 2 Entry Catalyst CEESO Turnovers^(a) 1 AgNO₃ 0.42 2Ag_(x)H_(5−x)PV₂Mo₁₀O₄₀ 8.13 3 Ag_(x)H_(4−x)PVMo₁₁O₄₀ 1.18 4Na₅PV₂Mo₁₀O₄₀ 0.00 5 K₅CoVW₁₁O₄₀ 0.00 6 K₅Cu^(II)PW₁₁O₃₉ 15.33 7Ag_(x)K_(12−x)Ce(PW₁₁O₃₉)₂ 4.47 8 (NH₄)₂Ce(NO₃)₆ 18.53 9Ag_(x)K_(5−x)Cu^(II)PW₁₁O₃₉ 15.21 ^(a)Turnovers = (mol of CEESO/mol ofcatalyst) × 100

Example 4 Aerobic Oxidation of Acetaldehyde Catalyzed byPolyoxometalates

In a 20 mL vial, 0.961 mmol acetaldehyde, 2 mg of POM, and pentane(internal standard) (34.7 μL) were stirred in 2 mL of chlorobenzeneunder 20 mL (0.82 mmol) of O₂ at 298 K for 24 hours. Under theseconditions, the POM was totally insoluble at all times during thereaction. For the cloth samples, the polyoxometalate was deposited as a5% by weight solution of H₂O and subsequently dried. BHT(2,6-di-tert-butyl-p-cresol) was used as a radical inhibitor in a 1.2mol ratio versus POM. The aerobic oxidation of acetaldehyde by the POMsis shown in Table 3.

TABLE 3 Time Equivalents % Conversion of % Yield Entry Catalyst (h)CH₃CHO^(a) Acetaldehyde^(b) Acetic Acid^(c) Turnovers^(d) 1 Blank 24 — 80 — 2 Na₈Co₂W₁₁O₃₉ 24 1538 97.8 67.2 1033 3 K₈SiCoVW₁₀O₃₉ 24 1521 95.760.2 916 4 K₇SiCoVW₁₀O₃₉ 24 1483 92.3 55.8 827 5 Blank 28.5 — 37 10 — 6Na₈Co₂W₁₁O₃₉ 28.5 3075 80.3 70.3 1844 7 K₈SiCoVW₁₀O₃₉ 28.5 3041 72.159.4 1491 7 K₇SiCoVW₁₀O₃₉ 28.5 2966 73.3 62.4 1545 8 Cotton-Na₈Co₂W₁₁O₃₉24 1538 98.2 66.2 815 9 Cotton-K₈SiCoVW₁₀O₃₉ 24 1521 90.4 50.0 644 10 1Na₈Co₂W₁₁O₃₉/1.2 BHT 24 1538 17.8 22.4 180 ^(a)Equivalents ofAcetaldehyde = moles of acetaldehyde (material)/moles of POM. For thelast three reactions (Entries 5-8) after 24 h another 0.961 mmolacetaldehyde was added, and the suspension was allowed to stir for anadditional 8 h. All values are averages of two experiments. ^(b)%Conversion = (moles of acetaldehyde consumed/moles of initialacetaldehyde) × 100. ^(c)% Yield = (moles of acetic acid/moles ofinitial acetaldehyde) × 100. ^(d)Turnovers = [moles of acetic acid (inthe run with catalyst) − moles of acetic acid (in the blank run withoutcatalyst)]/moles of catalyst.

Example 5 Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase byModified Polyoxometalates and Metal Compounds

Tetrahydrothiophene (THT) (0.445 mmol, 0.64 M) and 1,3-dichlorobenzene(internal standard) in the presence or absence of the polyoxometalateand/or metal compound were stirred in 4 mL of acetonitrile in 20 mLvials under 1 atm O₂ at room temperature. The aerobic oxidation of THTby modified polyoxometalates and metal compounds is shown in Table 4. InEntries 3-7 and 12, 2×10⁻⁶ mol of polyoxometalate or metal compound wasplaced in the vial before adding the reagent and internal standard. InEntries 8-14, the polyoxometalate and metal compound (Entries 11 and 14)or the metal compounds were placed in the vial before the addition ofthe reagent and the internal standard. In Entries 8-14, 2×10⁻⁶ mol ofeach POM or metal compound was used in a 1/1 ratio.

TABLE 4 Entry Catalyst Time (h) Yield %^(a) Turnover^(b) 1 Blank^(c) 3.50 — 2 Blank^(c) 72^(d )   0 — 3 H₅PV₂Mo₁₀O₄₀ 3.5 0 0 4 HAuCl₄ 3.5 0 0 5HAuCl₄ 72^(d )   0 0 6 (NH₄)₂Ce(NO₃)₆ 3.5 14 12 7 (NH₄)₂Ce(NO₃)₆72^(d )   26 100 8 (NH₄)₂Ce(NO₃)₆ + 3.5 14 12 H₅PV₂Mo₁₀O₄₀ 9(NH₄)₂Ce(NO₃)₆ + 3.5 67 57 HAuCl₄ 10 (NH₄)₂Ce(NO₃)₆ + 72^(d )   76 293HAuCl₄ 11 (NH₄)₂Ce(NO₃)₆ + 3.5 65 56 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 12 H₂PtCl₆3   0 0 13 (NH₄)₂Ce(NO₃)₆ + 3   25 21 H₂PtCl₆ 14 (NH₄)₂Ce(NO₃)₆ + 3   2623 H₂PtCl₆ + H₅PV₂Mo₁₀O₄₀ ^(a)Moles of THTO/moles of initial THT.^(b)Moles of THTO/moles of catalyst. ^(c)No catalysts. ^(d)More THT andO₂ added to the reaction system after 24 hr of initial reaction.

Example 6 Aerobic Oxidation of CEES in Liquid Phase by ModifiedPolyoxometalates and Metal Compounds

CEES (0.337 mmol, 0.64 M) and 1,3-dichlorobenzene (internal standard) inthe presence or absence of the polyoxometalate and/or metal compoundwere stirred in 4 mL of acetonitrile in 20 mL vials under 1 atm of O₂ atroom temperature. The aerobic oxidation of CEES by modifiedpolyoxometalates and metal compounds is shown in Table 5. In Entries 2,3, 5, and 6, 2×10⁻⁶ mol of polyoxometalate or metal compound was placedin the vial before adding the reagent. In Entries 4 and 7-12, thepolyoxometalate and/or the metal compound(s) (2×10⁻⁶ mol) were placed inthe vial before adding the reagent solution.

TABLE 5 Time Conversion Entry Catalyst (day) %^(a) Yield %^(b)Turnover^(c) 1 Blank^(d) 3 0 0 — 2 HAuCl₄ 3 0 0 0 3 H₅PV₂Mo₁₀O₄₀ 3 1 0 04 HAuCl₄ + 3 12 3 2 H₅PV₂Mo₁₀O₄₀ 5 (NH₄)₂Ce(NO₃)₆ 1 16 8 5 6(NH₄)₂Ce(NO₃)₆ 3 26 18 12 7 (NH₄)₂Ce(NO₃)₆ + 1 28 9 6 HAuCl₄ 8(NH₄)₂Ce(NO₃)₆ + 3 57 36 24 HAuCl₄ 9 (NH₄)₂Ce(NO₃)₆ + 1 47 24 15H₅PV₂Mo₁₀O₄₀ 10 (NH₄)₂Ce(NO₃)₆ + 3 64 41 27 H₅PV₂Mo₁₀O₄₀ 11(NH₄)₂Ce(NO₃)₆ + 1 53 43 28 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 12 (NH₄)₂Ce(NO₃)₆ + 382 70 46 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ ^(a)Moles of CEES consumed/moles ofinitial CEES. ^(b)Moles of CEESO (the GC response factor of CEESO isassumed the same as that of CEES)/moles of initial CEES. ^(c)Moles ofCEESO (the GC response factor of CEESO is assumed the same as that ofCEES)/moles of catalyst. ^(d)No catalyst.

Example 7 Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalateand HAuCl₄

Each POM (9.61×10⁻⁶ mol); HAuCl₄ (4.8×10⁻⁵ mol); 1,3-dichlorobenzene(9.61×10⁻⁴ mol), and CEES (9.61×10⁻⁴ mol) were stirred in 4 mL ofacetonitrile under 20 mL (0.82 mmol) of O₂ at 298 K. The aerobicoxidation is shown in Table 6.

TABLE 6 Time Turnovers^(a) Time Turnovers^(b) Entry Catalyst (h) ofCEESO (h) of CEESO 1 Na₄PVMo₁₁O₄₀ 4 0 11 1.1 2 Na₅PV₂Mo₁₀O₄₀ 4 5.0 1110.6 3 Na₆PV₃Mo₉O₄₀ 4 7.0 11 18.3 4 Na₅H₂PV₄W₈O₄₀ 4 4.4 11 14.2 5Na₉PV₆Mo₆O₄₀ 4 5.6 11 20.7 6 Na₅CuPW₁₁O₃₉ 4 59.2 11 83.6 7 HAuCl₄ 4 0 110 ^(a)Turnovers = (moles of CEESO (catalyst run) − moles of CEESO (blankrun))/moles of catalyst.

Example 8 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO)Using AgNO₃/HAuCl₄ System (Non-POM System)

A metal compound solution was prepared by combing AgNO₃ (1.0×10⁻⁵ mol)and HAuCl₄ (5.0×10⁻⁶ mol) in 1 mL of acetonitrile. To this solution wasadded CEES (3.0×10⁻³ mol). Upon addition of CEES to the solution, awhite precipitate immediately formed. The precipitate is believed to bea silver containing salt, possibly coordinated to CEES. The solution wasallowed to stir for 100 hours, at which time there was loss of CEES inthe solution based on gas chromatography. The filtrate was taken todryness, and a solution containing excess CEES in acetonitrile was addedto the yellow oily residue. Gas chromatography of the solution confirmedthe formation of CEESO. The results are shown in Table 7 (entries 1-7).

Example 9 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO)Using AgNO₃/AgClO₄/HAuCl₄ System (Non-POM System)

A 20 mL vial fitted with a PTFE septum was purged with 1 atm of O₂. Tothis vial were added by syringe, 0.035 mL of AgNO₃ (0.1013 M inacetonitrile); 0.060 mL of AgClO₄ (0.1138M in acetonitrile); and 0.100mL HAuCl₄ (0.0477 M in acetonitrile), and the total volume was adjustedto 1 mL with the addition of HPLC grade acetonitrile. To this solution,0.36 mL (2.86×10⁻³ mol) of CEES were added to the solution, and theformation of CEESO was monitored over time by gas chromatography using1,3-dichlorobenzene as the internal reference. The results aresummarized in Table 7 (Entries 8-11).

TABLE 7 Time Entry Catalyst (hrs) Turnover^(a) 1 2 AgNO₃ 100 0 2 2AgClO₄ 100 0 3 1 HAuCl₄ 100 0.9 4 2 AgNO₃ + 1 HAuCl₄ 1 13.0 5 2 AgNO₃ +1 HAuCl₄ 2 21.3 6 2 AgNO₃ + 1 HAuCl₄ 24 83.5 7 2 AgNO₃ + 1 HAuCl₄ 100146.3 8 0.75 AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 1 38.3 9 0.75 AgNO₃ + 1.25AgCl₄ + 1 HAuCl₄ 2 50.2 10 0.7 5AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 24 141.911 0.7 5AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 100 208.7 ^(a)Moles of CEESO/molesof catalyst (catalyst is based on moles of HAuCl₄ used).

Example 10 Aerobic Oxidation of CEES by POM/HAuCl₄ and MetalCompound/HAuCl₄ Systems

One equivalent of the POM or metal compound was combined with fiveequivalents of HAuCl₄ in acetonitrile, wherein the total volume was 1mL. To this solution, 100 equivalents of CEES was added. The reactionwas conducted under one atm of O₂ at 298 K. The number of turnovers werecalculated at 4 and 11 hours, and the results are summarized in Table8a.

TABLE 8a Turn- Entry POM or Metal Compound Turnovers^(a) overs^(b) 1Na₉PV₆Mo₆O₄₀ 5.6 20.7 2 Na₅CuPW₁₁O₃₉ 59.2 83.6 3 Na₅MnPW₁₁O₃₉ 6.5 29.0 4K₅CoPW₁₁O₃₉ 38.9 71.9 5 (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂ 5.1 27.9 6 K₅PMnW₁₁O₃₉51.8 76.5 7 Na₅PV₂Mo₁₀O₄₀ 5.0 10.6 8 Na₆PV₃Mo₉O₄₀ 7.0 18.3 9Na₅H₂PV₄Mo₈O₄₀ 4.4 14.2 10 K₁₂Cu₃(W₉PO₃₄)₂ 5.1 12.2 11 Na₄PVW₁₁O₃₉ 1.68.7 12 Na₅FeSiW₁₁O₄₀ 0.9 4.6 13 Na₅SiVW₁₁O₄₀ 0.0 2.3 14 K₁₀Ni₄P₂W₁₇O₆₁3.5 7.5 15 K₈Co(II)P₂W₁₇O₆₁ 1.0 2.5 16 K₁₂Pd₃(PW₉O₃₄)₂ 4.2 6.4 17K₈Cu(II)P₂W₁₇O₆₁ 2.0 4.7 18 Na₄PVMo₁₁O₄₀ 0.0 1.2 19 Na₃PMo₁₂O₄₀ 0.0 0.120 H₅PV₂W₁₀O₄₀ 0.0 1.4 21 H₆PV₃W₉O₄₀ 0.0 1.2 22 H₇PV4W₈O₄₀ 0.0 0.9 23HAuCl₄ 0.0 0.0 24 Na₁₆P₄W₃₀Cu₄O₁₁₂ 1.5 1.5 25H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂] 1.0 1.6 26 K₁₀Ce(PW₁₁O₃₉)₂ 0.6 0.727 K₇CuSiW₁₁O₃₉ 1.0 1.1 28 K₈CoVW₁₁O₄₀ 1.3 1.1 29 K₈Co₂W₁₁O₃₉ 1.5 1.0 30Na₇CuSiW₁₁O₃₉ 1.1 1.1 31 Na₅NiPW₁₁O₃₉ 0.6 0.9 32 Na₆SiVNbW₁₁O₃₉ 0.7 0.633 K₆SiTiW₁₁O₄₀ 0.6 0.4 34 K(NH₄)₆RuBW₁₁O₃₉ 0.7 0.9 35 Na₃AsW₁₂O₄₀ 0.70.2 36 K₆FeSiW₁₁O₃₉ 0.9 0.7 37 K₈NiP₂W₁₇O₆₁ 0.9 0.9 38(Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 1.8 1.9 39 K₁₀Co₄P₂W₁₈O₆₈ 1.3 1.6 40 Na₃V₁₀O₂₈1.8 1.7 41 K₁₀Mn₄(PW₉O₃₄)₂ 1.3 1.4 42 K₈P₂W₁₇(NbO₂) 1.1 0.9 43(NH₄)₆P₂FeW₁₇O₆₁ 0.6 0.5 44 K₇Mn(II)P₂W₁₇O₆₁ 1.0 0.8 45 K₁₀P₂W₁₈Cu₄O₆₈1.2 1.9 46 K₅Si(NbO₂)W₁₁O₄₀ 0.9 0.7 47 K₁₂P₂W₁₈Ni₃O₆₈ 1.0 1.8 48Na₃H₃Mo₉O₃₄ 0.8 0.9 49 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 1.1 1.4 50 (NH₄)₆P₂W₁₈O₆₂ 0.00.3 51 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 0.5 1.8 52 CuCl₂ 0.0 0.4 53 FeCl₃ 0.3 0.5^(a)Turnovers after 4 hours ^(b)Turnovers after 11 hours

Additional POM and/or metal compounds that were tested can be found inTable 8b.

TABLE 8b Entry Compound A Compound B 1 5 HAuCl₄ 2 Na₄PVMo₁₁O₄₀ 3Na₄PVMo₁₁O₄₀ 5 HAuCl₄ 4 Na₅PV₂Mo₁₀O₄₀ 5 Na₅PV₂Mo₁₀O₄₀ 5 HAuCl₄ 6Na₆PV₃Mo₉O₄₀ 7 Na₆PV₃Mo₉O₄₀ 5 HAuCl₄ 8 Na₅H₂PV₄Mo₈O₄₀ 9 Na₅H₂PV₄Mo₈O₄₀ 5HAuCl₄ 10 Na₉PV₆Mo₆O₄₀ 11 Na₉PV₆Mo₆O₄₀ 5 HAuCl₄ 12 Na₄PVW₁₁O₄₀ 13Na₄PVW₁₁O₄₀ 5 HAuCl₄ 14 Na₃PMo₁₂O₄₀ 15 Na₃PMo₁₂O₄₀ 5 HAuCl₄ 16Na₅CuPW₁₁O₃₉ 5 HAuCl₄ 17 (TBA)₅CuPW₁₁O₃₉ 5 HAuCl₄ 18 Na₅MnPW₁₁O₃₉ 19Na₅MnPW₁₁O₃₉ 5 HAuCl₄ 20 Na₅FeSiW₁₁O₃₉ 21 Na₅FeSiW₁₁O₃₉ 22 Na₅SiVW₁₁O₄₀23 Na₅SiVW₁₁O₄₀ 5 HAuCl₄ 24 Na₅PV₂W₁₀O₄₀ 25 Na₅PV₂W₁₀O₄₀ 5 HAuCl₄ 26Na₆PV₃W₉O₄₀ 27 Na₆PV₃W₉O₄₀ 5 HAuCl₄ 28 Na₇PV₄W₈O₄₀ 29 Na₇PV₄W₈O₄₀ 5HAuCl₄ 30 Na₁₆P₄W₃₀Cu₄O₁₁₂ 31 Na₁₆P₄W₃₀Cu₄O₁₁₂ 5 HAuCl₄ 32H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂ 33 H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅6)₂5 HAuCl₄ 34 K₁₀Ce(PW₁₁O₃₉)₂ 35 K₁₀Ce(PW₁₁O₃₉)₂ 5 HAuCl₄ 36 K₇CuSiW₁₁O₃₉37 K₇CuSiW₁₁O₃₉ 5 HAuCl₄ 38 K₈CoVW₁₁O₃₉ 39 K₈CoVW₁₁O₃₉ 5 HAuCl₄ 40K₅CoPW₁₁O₃₉ 41 K₅CoPW₁₁O₃₉ 5 HAuCl₄ 42 K₈Co₂W₁₁O₃₉ 43 K₈Co₂W₁₁O₃₉ 5HAuCl₄ 44 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 45 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 5 HAuCl₄ 46Na₇CuSiW₁₁O₃₉ 47 Na₇CuSiW₁₁O₃₉ 5 HAuCl₄ 48 Na₅NiPW₁₁O₃₉ 49 Na₅NiPW₁₁O₃₉5 HAuCl₄ 50 Na₆SiVNbW₁₁O₃₉ 51 Na₆SiVNbW11O₃₉ 5 HAuCl₄ 52 K₅PMnW₁₁O₃₉ 53K₅PMnW₁₁O₃₉ 5 HAuCl₄ 54 K₆SiTiW₁₁O₄₀ 55 K₆SiTiW₁₁O₄₀ 5 HAuCl₄ 56K(NH₄)₆RuBW₁₁O₃₉ 57 K(NH₄)₆RuBW₁₁O₃₉ 5 HAuCl₄ 58 Na₃AsW₁₂O₄₀ 59Na₃AsW₁₂O₄₀ 5 HAuCl₄ 60 K₆FeSiW₁₁O₃₉ 61 K₆FeSiW₁₁O₃₉ 5 HAuCl₄ 62K₈NiP₂W₁₇O₆₁ 63 K₈NiP₂W₁₇O₆₁ 5 HAuCl₄ 64 (Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 65(Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 5 HAuCl₄ 66 K₁₀Co₄P₂W₁₈O₆₈ 67 K₁₀Co₄P₂W₁₈O₆₈ 5HAuCl₄ 68 Na₃V₁₀O₂₈ 69 Na₃V₁₀O₂₈ 5 HAuCl₄ 70 K₁₀(Mn₄)(PW₉O₃₄)₂ 71K₁₀(Mn₄)(PW₉O₃₄)₂ 5 HAuCl₄ 72 K₁₂Cu₃(W₉PO₃₄)₂ 73 K₁₂CU₃(W₉PO₃₄)₂ 5HAuCl₄ 74 K₁₀Ni₄P₂W₁₇O₆₁ 75 K₁₀Ni₄P₂W₁₇O₆₁ 5 HAuCl₄ 76 K₈P₂W₁₇(NbO₂) 77K₈P₂W₁₇(NbO₂) 5 HAuCl₄ 78 (NH₄)₆P₂FeW₁₇O₆₁ 79 (NH₄)₆P₂FeW₁₇O₆₁ 5 HAuCl₄80 K₈Co(II)P₂W₁₇O₆₁ 81 K₈Co(II)P₂W₁₇O₆₁ 5 HAuCl₄ 82 K₁₂Pd₃(PW₉O₃₄)₂ 83K₁₂Pd₃(PW₉O₃₄)₂ 5 HAuCl₄ 84 K₇Mn(II)P₂W₁₇O₆₁ 5 HAuCl₄ 85 K₁₀P₂W₁₈Cu₄O₆₈5 HAuCl₄ 86 K₈Cu(II)P₂W₁₇O₆₁ 5 HAuCl₄ 87 K₅Si(NbO₂)W₁₁O₄₀ 5 HAuCl₄ 88K₁₂P₂W₁₈Ni₃O₆₈ 5 HAuCl₄ 89 Na₃H₆Mo₉O₃₄ 5 HAuCl₄ 90 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 5HAuCl₄ 91 (NH₄)₆P₂W₁₈O₆₂+5HAuCl₄ 5 HAuCl₄ 92 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 5HAuCl₄ 93 5 Cu(acetate)₂ 94 Na₅PV₂Mo₁₀O₄₀ 5 Cu(acetate)₂ 95 5 Co(II)Acac96 Na₅PV₂Mo₁₀O₄₀ 5 Co(II)Acac 97 5 Fe(III)Acac 98 Na₅PV₂Mo₁₀O₄₀ 5Fe(III)Acac 99 5 MnO₂ 100 Na₅PV₂Mo₁₀O₄₀ 5 MnO₂ 101 5 CuCl₂ 102Na₅PV₂Mo₁₀O₄₀ 5 CuCl₂ 103 5 FeCl₃ 104 Na₅PV₂Mo₁₀O₄₀ 5 FeCl₃ 105 5 CrCl₃106 Na₅PV₂Mo₁₀O₄₀ 5 CrCl₃ 107 5 CeCl₃ 108 Na₅PV₂Mo₁₀O₄₀ 5 CeCl₃ 109Na₉PV₆Mo₆O₄₀ 5 FeCl₃ 110 Na₉PV₆Mo₆O₄₀ 5 CuCl₂ 111 Na₉PV₆Mo₆O₄₀ 112K₁₂Pd₃(PW₉O₃₆)₂ 5 FeCl₃ 113 K₁₂Pd₃(PW₉O₃₆)₂ 5 CuCl₂ 114 K₁₂Pd₃(PW₉O₃₆)₂115 Na₅CuPW₁₁O₃₉ 116 Na₅CuPW₁₁O₃₉ 5 Cr(NO₃)₃ 117 5 CrNO₃ 118Na₅CuPW₁₁O₃₉ 5 Co(NO₃)₂ 119 5 Co(NO₃)₂ 120 5 Zn(NO₃)₂ 121 Na₅CuPW₁₁O₃₉ 5Zn(NO₃)₂ 122 Na₅CuPW₁₁O₃₉ 5 CU(NO₃)₂ 123 5 Cu(NO₃)₂ 124 Na₅CuPW₁₁O₃₉ 5Zn(NO3)3 125 Na₅CuW₁₁O₃₉ 5 Cu(acetate)₂ 126 Na₅CuW₁₁O₃₉ 5 Fe(acetate)₂127 Na₅CuW11O₃₉ 5 MnO₂ 128 5 NaNO₃ 129 Li₅PVW₁₁O₄₀ 5 HAuCl₄ 130 AgNO₃131 AgNO₃ 5 HAuCl₄ 132 NaNO₃ 5 HAuCl₄ 133 NaClO₄ 5 HAuCl₄ 134 AgClO₄ 5HAuCl₄ 135 LiClO₄ 5 HAuCl₄ 136 5 (NH₄)₂Ce(NO₃)₆ 137 Na₅PVMo₁₁O₄₀ 5(NH₄)₂Ce(NO₃)₆ 138 Na₅CuPW₁₁O₃₉ 5 (NH₄)₂Ce(NO₃)₆ 139 Na₅PVMo₁₁O₄₀ 5CoSO₄ 140 Na₅CuPW₁₁O₃₉ 5 CoSO₄ 141 Na₅PVMo₁₁O₄₀ 5 Ce(SO₄)₂ 142Na₅CuPW₁₁O₃₉ 5 Ce(SO₄)₂ 143 Na₅PVMo₁₁O₄₀ 5 H₂PtCl₆ 144 Na₅CuPW11O₃₉ 5H₂PtCl₆ 145 Na₅PVMo₁₁O₄₀ 5 Pd(NO₃)₂ 146 Na₅CuPW₁₁O₃₉ 5 Pd(NO₃)₂ 147Na₅PVMo₁₁O₄₀ 5 RhCl₃ 148 Na₅CuPW₁₁O₃₉ 5 RhCl₃ 149 Na₅PVMo₁₁O₄₀ 5 ReO₂150 Na₅CuPW₁₁O₃₉ 5 ReO₂

Example 11 Oxidation of CEES to CEESO by Metal Compounds (Non-POM)

(a) Determining the Stoichiometry of O, in the Catalytic Oxidation ofCEES. A Schlenk flask fitted with septum was attached to a manometer andpurged with O₂. To the flask containing 1.36 mL of acetonitrile,solutions (all in acetonitrile) of 0.200 mL of (NEt₄)AuCl₂ (5.0×10⁻⁶mol), 0.188 mL of AgClO₄ solution (1.0×10⁻⁵ mol), 0.094 mL NBu₄NO₃solution (5.0×10⁻⁶ mol), 0.166 mL 1,3-dichlorobenzene (7.5×10⁻⁴ mol)(internal standard for GC), and 0.084 mL CEES (3.8×10⁻⁴ mol) were added.The consumption of O₂ was recorded, and aliquots were periodically takenand injected into the GC. The stoichiometry of O₂ consumption wasestablished using a manometer to determine the amount of O₂ consumedwhile simultaneously monitoring CEESO formation with a gas chromatographFIG. 1 reveals that one equivalent of the CEESO formed corresponds to0.5 equivalents of O₂.

(b) Cream Formulation Reactions. Experiments were-performed using theperfluorinated oil. Galden DO2, and Fomblin perfluorinated polyether oilas “solvent,” both of which are components of the cream. Samples wereprepared by adding components together, dissolving in a minimal amountof acetonitrile, stirring for 10 minutes, and then removing the solventby vacuum.

In all the cases where (NEt₄)AuCl₂ was used as the gold compound,1.25×10⁻⁵ mol of the gold compound was used. The other components whichwere varied in quantities were NBu₄NO₃ (1.25×10⁵-1.25×10⁻⁴ mol); and aCuSO₄ (1.25×10⁻⁵-1.25×10⁻⁴ mol) (Table 9). The gold, copper, and/ornitrate salts were admixed in acetonitrile, then the solvent was removedby vacuum. After the mixture was dried by vacuum in a Schlenk flask, theflask is attached to the manometer and the apparatus is purged with O₂.After purging, 7.0 mL of the perfluorinated fluid was added to theflask. The system was equilibrated to atmospheric pressure then sealedfrom any external atmosphere. Through the septum 0.05 mL (4.2×10⁻⁴ mol)of CEES was added and the system was monitored for O₂ consumption. Table9 shows CEESO formation after 1 hour using various cream formulations(7.0 mL Galden DO2).

TABLE 9^(a) [Au] [NO₃] [Cu⁺²] [CEESO formed] 0 1.25 1.25 3.62 1.25 1.251.25 5.80 0 2.50 2.50 5.00 1.25 2.50 2.50 8.06 0 5.00 7.25 8.06 1.255.00 7.25 16.20 0 10.00 12.50 10.60 1.25 10.00 12.50 18.70 ^(a)Allconcentrations expressed in 10⁻⁵ mol.

Another experiment was performed using Fomblin as the “solvent.” In thiscase, 1.0 mL of Fomblin, 0.005 g of (NEt₄)AuCl₂ (1.25×10⁻⁵ mol), wasadmixed in with varying amounts of CuSO₄, MnSO₄, VOSO₄, Ti(SO₄)₂,Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃,and/or NBu₄NO₃. The catalyst was prepared and the experiment wasperformed using the same method as earlier reported. Table 10 revealsCEESO formation in PFPE Surfactant (1.0 mL Fomblin) using various metalcompounds. The metal compounds are abbreviated for simplicity sake. Forexample, metal compound 1Au/1Cu(II)/1NO₃ was prepared by mixing oneequivalent each of (NEt₄)AuCl₂, CuSO₄, and NBu₄NO₃.

TABLE 10 Turnovers of CEESO after 10 min Metal Compound (based on Au)1Au/1Cu(II)/1NO₃ 17 1Au/2Cu(II)/1NO₃ 28 1Au/1Cu(II)/2NO₃ 1151Au/2Cu(II)/2NO₃ 155 1Au/1Cu(II)/3NO₃ 155 1Au/1Fe(III)/3NO₃ 1421Au/2Mn(II)/3NO₃ 164 1Au/2Ti(IV)/3NO₃ 142 1Au/2Co(II)/3NO₃ 177 1Au/4NO₃185 1Au/2Cu(II)/3NO₃ 181 1Au/2Cu(II)/4NO₃ 195 1Au/3Cu(II)/3NO₃ 1652Cu(II)/3NO₃ 28 1Au/3NO₃ 150 1Fe(III)/3NO₃ 19 1Au/2V(IV)/3NO₃ 1601Au/2Ni(II)/3NO₃ 140 1Au/2Ag(II)/3NO₃ 184

FIG. 2 shows CEESO formation as a function of time for 1Au/2Cu(II)₃NO₃,2Cu(II)/3NO₃, and 1Au/3NO₃. From the data in Table 10 and FIG. 2, it isclear that there was a synergistic effect when certain redox activemetals were added to the Au/NO₃ system. For example, one of the mostactive systems, 1Au/2Cu(II)₁₋₃NO₃ was 3.8 and 6.5 times more effectiveafter 10 minutes of reaction time than when only 2 of the componentswere used, 1Au/3NO₃ and 2Cu(II)/3NO₃ respectively. Also, FIG. 2 showsthat inhibition was less pronounced in the three component system.Another important aspect of this system is that the oxidation terminatesto the sulfoxide without continued oxidation to yield the sulfone. Thisis important as it relates to toxicity issues as it is believed that thesulfoxide of mustard gas is significantly less toxic than thecorresponding sulfone.

Example 12 Synthesis, Characterization, and Reactivity ofOrgano-Modified POMs (a) Synthesis of Ag₂[V₆O₁₃((OCH₂)₃CCH₃)₂] (Ag MeCap)

Na₂[V₆O₁₃((OCH₂)₃OCH₃)₂] (Na Me cap, 0.480 g) was dissolved in ˜4 mL ofdistilled water. This was filtered over a medium fritted funnel toremove any undissolved POM. To the dark red-orange solution was addedAgNO₃ (0.215 g) with stirring. An orange-red precipitate formedimmediately. The crude product was separated by suction filtration overa medium frit, washed with room temperature water and ether. The productwas dried over night in vacuo. Crystals were grown by diffusing etherinto an acetonitrile solution of the crude product at room temperature.⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN) −499.232 ppm (singlet).Solid-state IR (KBr pellet, 1400-400 cm⁻¹) 1452.11 (m), 1390.47 (w),1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs), 820.36 (sh), 794.68(s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

(b) Synthesis of Co[V₆O₁₃((OCH₂)₃CCH₃)₂] (Co Me Cap)

The same procedure for the synthesis of Ag₂-[V₆O₁₃((OCH)₃CCH₃)₂] wasfollowed, except CoCl₂ was added to form the Co salt of the POM.Crystals were grown from diffusing isopropyl alcohol into a MeCNsolution of crude product. ⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN)−500.3 ppm (singlet). Solid-state IR (KBr pellet, 1400-400 cm⁻¹) 1452.11(m), 139-0.47 (w), 1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs),820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

(c) Reactivity of Organo-Modified POMs

Table 11 lists the oxidation of tetrahydrothiophene (THT) byt-butylhydroperoxide (TBHP) catalyzed by the transition metal salts ofMe-capped V₆O₁₃. The oxidations were performed by dissolving theparticular salt in acetonitrile to give lightly colored orange-yellowsolutions. The solutions were placed in 24-mL vials fitted with PTFEsepta. THT and TBHP were then syringed in and the reactions weremonitored by quantitative GC. Reactions were stirred at roomtemperature.

TABLE 11 Room Temperature Oxidation of THT to THTO by TBHP Catalyzed byTransition Metal Salts of Me Capped V₆O₁₃ after 48 Hours. Mols of Molsof Turnover Catalyst catalyst, ×10⁻⁶ THTO, ×10⁻⁵ number^(b) Na Me cap1.76 6.03 34.3 Ag Me cap 1.87 5.59 30.0 Co Me cap 1.61 6.33 39.3 AgNO₃14.1 1.06 0.754 CoCl₂ 39.5 2.25 0.570 blank^(a) NA 0 0 ^(a)blankreaction: 3.0 mL of MeCN, 0.018 mL of THT, 0.010 mL of internalreference. ^(b)Turnover number = (mols of THTO)/(mols of catalyst) × 100

Throughout this application, various publications are referenced. Thedisclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the state of the art to which this invention pertains.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only.

1-64. (canceled)
 65. A modified material for removing a contaminant froman environment, wherein the modified material comprises (1) a materialcomprising a topical carrier. a powder, a coating, or a fabric, and (2)a metal compound comprising a transition metal compound, an actinidecompound, a lanthanide compound, or a combination thereof, wherein themetal compound is not a polyoxometalate.
 66. The modified material ofclaim 65, wherein the metal compound comprises a cerium compound, aplatinum compound, a silver compound, a gold compound, or a combinationthereof.
 67. The modified material of claim 65, wherein the metalcompound is a gold compound.
 68. The modified material of claim 65,wherein the metal compound is a platinum compound.
 69. The modifiedmaterial of claim 65, wherein the metal compound is a cerium compound.70. The modified material of claim 65, wherein the metal compound is asilver compound.
 71. The modified material of claim 65, wherein themetal compound is a cerium compound and a platinum compound.
 72. Themodified material of claim 65, wherein the metal compound is a ceriumcompound and a gold compound.
 73. The modified material of claim 65,wherein the metal compound is a silver compound and a gold compound. 74.The modified material of claim 65, wherein the material is a topicalcarrier and the metal compound is a silver compound.
 75. The modifiedmaterial of claim 65, wherein the topical carrier is aperfluoropolyether and the metal compound is a silver compound, a goldcompound, or a combination thereof.
 76. The modified material of claim65, wherein the topical carrier is a perfluoropolyether and the silvercompound is AgNO₃, AgClO₄, or a combination thereof.
 77. The modifiedmaterial of claim 65, wherein the metal compound comprises (1) gold,copper, and nitrate; (2) gold, iron, and nitrate; (3) gold, manganese,and nitrate; (4) gold, titanium, and nitrate; (5) gold, cobalt, andnitrate; (6) gold and nitrate; (7) copper and nitrate; (8) iron andnitrate; (9) gold, vanadium, and nitrate; (10) gold, nickel, andnitrate; (11) gold, silver, and nitrate; (12) gold, chloride, andnitrate; or (13) cerium compound.
 78. The modified material of claim 65,wherein the metal compound comprises gold, chloride, and nitrate. 79.The modified material of claim 65, wherein the metal compound comprisesmixing (1) (NEt₄,)AuCl₂ and (2) CUSO₄, MnSO₄, VOSO₄, Ti(SO₄)₂,Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃, orNBu₄NO₃, or a combination thereof.
 80. An article comprising themodified material of claim
 65. 81. A method for removing a contaminantfrom an environment, comprising contacting a modified material of claim65 with the environment containing the contaminant for a sufficient timeto remove the contaminant from the environment.